JP2002532581A - Catalyst compositions and methods for their preparation and use in polymerization processes - Google Patents

Abstract

  (57) [Summary] The present invention relates to a catalyst composition of a polymerization catalyst and a carbonyl compound and a method for producing a catalyst composition of a polymerization catalyst and a carbonyl compound. The invention also relates to the use of the catalyst composition in the polymerization of one or more olefins. In particular, the polymerization catalyst system is supported on a support. More particularly, the polymerization catalyst composition comprises a bulky ligand metallocene-type catalyst system.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to catalyst compositions and methods of making the catalyst compositions and their use in processes for polymerizing olefins. In particular, the present invention relates to a method for preparing a catalyst composition comprising a bulky ligand metallocene-type catalyst system and / or a conventional transition metal catalyst system, and a carbonyl compound.

[0002] Advances in the background polymerization and catalyst of the present invention resulted in the ability to produce many new polymers having physical and chemical properties which are useful improvements in a wide variety of superior products and applications. With the development of new catalysts, the choice of polymerization type (solution, slurry, high pressure or gas phase) to produce a particular polymer has been greatly expanded. Also, advances in polymerization technology have provided more efficient, highly productive and economically improved processes. Of particular note among these advances is the development of the art using bulky ligand metallocene-type catalyst systems. Despite these technological advances in the polyolefin industry, there are still common problems as well as new challenges related to process operability. For example, the tendency to form fouling and / or sheeting in a gas or slurry phase process remains a challenge.

For example, in a continuous slurry process, fouling on the walls of the reactor, which acts as a heat transfer surface, can lead to many operational problems. Poor heat transfer during polymerization can result in polymer particles sticking to the reactor walls. These polymer particles can continue to polymerize on the wall and can result in premature reactor shutdown. Also, depending on reactor conditions, some of the polymer may dissolve in the reaction diluent and redeposit, for example, on metal heat exchanger surfaces.

In a typical continuous gas phase process, a recycle system is used for a number of reasons, including the removal of heat generated during the process by polymerization. Contamination, sheeting, and / or generation of static electricity in a continuous gas phase process can result in inefficient operation of various reactor systems. For example, recirculation system cooling mechanisms, temperature probes used for process control, and distributor plates, if affected, can result in premature reactor shutdown.

[0005] Evidence of operational problems in various processes, and solutions to them, have been explored by many in the art. See, for example, U.S. Pat.
Nos. 592, 4,803,251, 4,855,370, and 5,39
No. 1,657 all discuss techniques for reducing the generation of static electricity in polymerization processes, for example by introducing water, alcohols, ketones and / or inorganic chemical additives into the process; EP 0 634 421. B1 discusses introducing water, alcohols and ketones directly into the polymerization process to reduce fouling. WO 97/14721, published April 24, 1997, discusses the addition of inert hydrocarbons to the reactor to control fines that can cause sheeting; US Patent 5,627,243 discusses a new type of distributor plate for use in a fluidized bed gas phase reactor; WO 96/08520 discloses the introduction of a scavenger into the reactor. Discusses avoiding;
U.S. Pat. No. 5,461,123 discusses the use of acoustic waves to reduce sheeting; U.S. Pat. No. 5,066,736 and EP-A1 0 549.
252 discuss the introduction of an activation retarder into a reactor to reduce agglomeration; U.S. Pat. No. 5,610,244 discusses the use of on-floor to prevent fouling and improve polymer quality. U.S. Pat. No. 5,126,414 relates to directly supplying make-up monomer to a reactor; U.S. Pat. No. 5,126,414 contains an oligomer removal system to reduce fouling of distributor plates and provide gel-free polymers. EP-A1 045 published October 23, 1991.
No. 3 116 discusses introducing an antistatic agent into the reactor to reduce the amount of sheets and agglomeration; U.S. Pat. No. 4,012,574 teaches a reactor to reduce fouling. U.S. Pat. No. 5,026,795 discusses adding an antistatic agent with a liquid carrier to a polymerization zone in a reactor. US Patent No. 5,4
No. 10,002 discusses the use of a conventional Ziegler-Natta-Titanium / Magnesium supported catalyst system in which selected antistatic agents are added directly to the reactor to reduce fouling; Patent Nos. 5,034,480 and 5,054
No. 34,481 discusses the reaction product of a conventional Ziegler-Natta-titanium catalyst and an antistatic agent to produce ultra-high molecular weight ethylene polymers; U.S. Pat. No. 3,082,198 describes hydrocarbons. Discusses introducing a carboxylic acid in an amount dependent on the amount of water in a process for the polymerization of ethylene using a titanium / aluminum organometallic catalyst in a liquid medium; and US Pat. No. 3,919,185.
No. 1 describes conventional Ziegler-Natta or Phillips type catalysts and at least 30
A slurry process using a non-polar hydrocarbon diluent using a polyvalent metal salt of an organic acid having a molecular weight of 0 is described.

Coating a polymerization apparatus, for example, treating a reactor wall with a chromium compound as described in US Pat. Nos. 4,532,311 and 4,876,320 Injecting various reagents into the process, for example, providing a soluble metallocene-type catalyst system that is not supported in a narrow area in a polymerization reactor and adding antifoulants or antistatic agents to the reactor; PCT Publication WO 97/46599 published December 11, 1997, discussing the injection into the reactor; controlling the polymerization rate, especially the starting polymerization rate; and modifying the reactor design There are various other known methods for improving operability, including:

Others in the art to improve process operability have discussed reforming catalyst systems by preparing the catalyst systems in different ways. For example, methods in this art include combining the components of the catalyst system in a particular order; manipulating the proportions of the various catalyst system components; changing the contact time and / or temperature when combining the catalyst system components. Or simply adding various compounds to the catalyst system. These techniques or combinations thereof are discussed in the literature. Particularly representative in the art are bulky ligand metallocene-type catalyst systems, more particularly supported bulky ligand metallocene-type catalysts with reduced fouling tendency and better operability. 2 is a preparation procedure and method for producing a system. Examples of these include: WO 96/11961 published April 26, 1996.
Discusses an antistatic agent as a component of a supported catalyst system to reduce fouling and sheeting in a gas, slurry, or liquid pool polymerization process; U.S. Pat. No. 5,283,218 discloses a metallocene catalyst. US Pat. Nos. 5,332,706 and 5,473,028 relied on special techniques for forming catalysts by initial impregnation; US Pat. Nos. 5,427,991 and No. 5,643,847 describes the chemical attachment of a non-coordinating anionic activator to a support; US Pat. No. 5,492,975 discusses a polymer-bound metallocene-type catalyst system. U.S. Pat. No. 5,661,095 discusses loading a metallocene-type catalyst on a copolymer of an olefin and an unsaturated silane;
PCT International Publication Pamphlet WO 97/061 published on February 20, 997
86 teaches the removal of inorganic and organic impurities after the formation of the metallocene-type catalyst itself; PCT publication WO 97/15602 published May 1, 1997 discloses an easily supported metal complex. 1997;
WO 97/27224 published July 31, 2014 relates to the formation of supported transition metal compounds in the presence of unsaturated organic compounds having at least one terminal double bond; and EP-A2-811 638 Discuss the use of metallocene catalysts and activating cocatalysts in a polymerization process in the presence of a nitrogen-containing antistatic agent.

Although all these possible solutions somewhat reduce the level of soiling or sheeting, some are expensive to use and / or continuous processes, especially commercial or large-scale processes Dirt and sheeting cannot be reduced to a level sufficient to drive the vehicle successfully.

[0009] It would therefore be advantageous to have a polymerization process that can be operated continuously with improved reactor operability and at the same time produce new and improved polymers. Also, more stable catalyst productivity, reduced soiling / seating tendency,
It would also be very beneficial to have a continuous operation polymerization process with extended operating time.

SUMMARY OF THE INVENTION The present invention provides a method for preparing a new and improved catalyst composition and its use in a polymerization process. The method comprises the steps of combining, contacting, blending, and / or mixing a catalyst system, preferably a supported catalyst system, with a carbonyl compound. In one aspect, the catalyst system comprises a conventional transition metal catalyst compound. In a most preferred embodiment, the catalyst system comprises a bulky ligand metallocene-type catalyst compound. The combination of the catalyst system and the carbonyl compound is useful in any olefin polymerization process. Preferred polymerization methods are gas phase or slurry phase methods, most preferably gas phase methods.

In one aspect, the invention is a method of making a catalyst composition useful for the polymerization of olefins, wherein the polymerization catalyst is combined, contacted, blended, and / or with at least one carbonyl compound. Or a method comprising mixing. In one embodiment, the polymerization catalyst is a conventional transition metal polymerization catalyst, more preferably a supported conventional transition metal polymerization catalyst. In a most preferred embodiment, the polymerization catalyst is a bulky ligand metallocene-type catalyst, most preferably a supported bulky ligand metallocene-type polymerization catalyst.

In one preferred embodiment, the present invention relates to a catalyst compound, preferably a conventional transition metal catalyst compound, more preferably a bulky ligand metallocene catalyst compound, an activator and / or cocatalyst, a carrier, and The present invention relates to a catalyst composition containing a carbonyl compound.

In the most preferred method of the present invention, the carbonyl compound is blended, preferably dry blended, and most preferably tumble dry blended or fluidized with a polymerization catalyst comprising a supported catalyst system or support. In this most preferred embodiment, the polymerization catalyst comprises at least one bulky ligand metallocene-type catalyst compound, activator, and carrier.

In yet another aspect, the invention relates to a method of polymerizing one or more olefins in the presence of a catalyst composition comprising a polymerization catalyst and a carbonyl compound, preferably wherein the polymerization catalyst comprises a carrier, more preferably The polymerization catalyst comprises one or more combinations of conventional catalyst compounds and / or metallocene catalyst compounds of bulky ligands.

[0015] In a preferred method of preparing the catalyst composition of the present invention, the method comprises a bulky ligand metallocene type catalyst compound, an activator, and a bulky ligand metallocene type supported in combination with a support. Forming a catalyst system and contacting the supported bulky ligand metallocene catalyst system with a carbonyl compound. In a most preferred embodiment, the supported bulky ligand metallocene-type catalyst system and the carbonyl compound are in a substantially dry or dry state.

In one aspect, the present invention provides a method of polymerizing one or more olefins in the presence of a combined, contacted, blended, or mixed polymerization catalyst with at least one carbonyl compound. I will provide a.

In another preferred embodiment, the present invention relates to a method for producing a carbonyl compound in a reactor wherein the carbonyl compound is introduced prior to the introduction of the polymerization catalyst and / or wherein the carbonyl compound is added to the reactor simultaneously with the polymerization catalyst. Methods for polymerizing one or more olefins are provided.

DETAILED DESCRIPTION OF THE INVENTION Introduction The present invention relates to a method for producing a catalyst composition and the catalyst composition itself. The present invention also relates to a polymerization process using the catalyst composition having improved operability and production capacity. Surprisingly, it has been found that the use of a carbonyl compound in combination with a catalyst system results in a substantially improved polymerization process. Particularly surprising is that when the catalyst system is supported on a support, when the catalyst system further comprises a bulky ligand metallocene-type catalyst system, and when the further bulky ligand metallocene-type catalyst is very This is the case when they are active and / or incorporate high levels of comonomers.

The use of the polymerization catalysts described below in combination with a carbonyl compound can result in substantial improvements in process operability, significant reduction in sheeting and fouling, improved catalytic performance, better polymer particles, and Provides the ability to produce a wider range of polymers.

All polymerization catalysts, including catalyst components and catalyst systems conventional transition metal catalysts, are suitable for use in the polymerization process of the present invention. However, the use of bulky ligands and / or bridged bulky ligands using metallocene-type catalysts is particularly preferred. The following is a non-limiting discussion of various catalysts useful in the present invention.

Conventional Transition Metal Catalysts Conventional transition metal catalysts are traditional Ziegler-Natta catalysts and Phillips-type chromium catalysts that are well known in the art. Examples of conventional transition metal catalysts are disclosed in U.S. Patent Nos. 4,115,639, 4,077,904, 4,482,687, 4,564,605, and 4,721,763. Nos. 4,879,359, and 4,960,741, all of which are fully incorporated herein by reference. Conventional transition metal catalyst compounds that can be used in the present invention include transition metal compounds from Groups III to VIII of the Periodic Table of the Elements, preferably Groups IVB to VIB.

These conventional transition metal catalysts can be represented by the formula: MR _x , wherein:
M is a metal from Groups IIIB to VIII, preferably Group IVB, more preferably titanium; R is a halogen or hydrocarbyloxy group; and x is the valency of the metal M. Non-limiting examples of R include alkoxy, phenoxy,
Bromide, chloride, and fluoride. Non-limiting examples of conventional transition metal catalysts where M is titanium are TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) ₃ C
1, Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₄ H ₉ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , TiCl ₃ . １ ／ AlCl ₃ , and Ti (OC ₁₂ H ₂₅ ) Cl ₃ .

Conventional based on magnesium / titanium electron donor complexes useful in the present invention
Type transition metal catalyst compounds are described, for example, in US Pat.
No. 302,566, which are fully incorporated herein by reference.
). MgTiCl₆(Ethyl acetate)₄Derivatives are particularly preferred
No. UK Patent No. 2,105,355 and US Patent No. 5,317,036 (reference
Are incorporated herein by reference) are various conventional vanadium catalysts
Compounds are described. A non-limiting example of a conventional vanadium catalyst compound is VOC
l₃, VOCl₂(OBu) (where Bu = butyl) and VO (OC₂H₅) ₃ Vanadyl trihalides, vanadyl alkoxy halides, and vanadyl alides such as
Coxide; VCl₄And VCl₃Vanadium tetrahalide such as (OBu)
And vanadium alkoxy halides; V (AcAc)₃And VOCl₂(AcAc)
(Where (AcAc) is acetylacetonate) and
Includes vanadyl acetylacetonate and chloroacetylacetonate. Preferred
A conventional vanadium catalyst compound is VOCl₃, VCl₄And VOCl₂In OR
Wherein R is a hydrocarbon group, preferably C₁Or C₁₀Aliphatic or aromatic
Hydrocarbon groups such as ethyl, phenyl, isopropyl, butyl, propyl, n
-Butyl, iso-butyl, tertiary butyl, hexyl, cyclohexyl, na-butyl
Futyl, others, and vanadium acetylacetonate.

Conventional chromium catalyst compounds, often referred to as Phillips type catalysts, suitable for use in the present invention are CrO ₃ , chromocene, silyl chromate, chromyl chloride (CrO ₂ Cl ₂ ), 2-ethyl-hexanoic acid Chromium, chromium acetylacetonate (Cr (AcAc) ₃ ) and the like. Non-limiting examples are described in U.S. Patent Nos. 3,709,853, 3,709,954, 3,231,550, 3,242,099, and 4,077,904. Is disclosed in
These are incorporated herein by reference.

Still other conventional transition metal catalyst compounds and catalyst systems suitable for use in the present invention are described in US Pat. Nos. 4,124,532, 4,302,565, 4,302,566. Nos. 4,376,062, 4,379,758, 5,066,737, and 5,763,723 and published EP-A2.
0 416 815 A2 and EP-A1 420 420 436, all of which are incorporated herein by reference. The conventional transition metal catalyst of the present invention can also have the general formula M ′ _t M ″ X _2t Y _u E, where M ′ is Mg, Mn, and / or Ca; M ″ is a transition metal Ti, V and / or Zr; X is a halogen, preferably Cl, B or I; Y is the same or different Well, M '
In an amount sufficient to satisfy the valence state of alone or oxygen, -NR ₂ , -OR, -SR,
-COOR or -OSOOR (where R is a hydrocarbyl group, especially an alkyl, aryl, cycloalkyl or arylalkyl group), halogen in combination with acetylacetonate; u is 0.5 E is an electron donor compound selected from the following classes of compounds: (a
A) esters of organic carboxylic acids, (b) alcohols, (c) ethers, (d) amines, (e) esters of carbonic acid, (f) nitriles, (g) phosphoramides, (h) esters of phosphoric and phosphorous acids, and (J) phosphorus oxychloride. Non-limiting examples of complexes satisfying the above formula include the _{following: MgTiCl 5 · 2CH 3 COOC 2} H 5,
_{Mg 3 Ti 2 Cl 12 · 7CH} 3 COOC 2 H 5, MgTiCl 5 · 6C 2 H 5 OH, MgTiCl 5 · 100CH 3 OH, MgTiCl 5 · _{tetrahydrofuran, MgTi 2 Cl 12 · 7C 6} H 5 CN, Mg 3 Ti 2 _{Cl 12 · 6C 6 H 5 COOC} 2 H 5, MgTiCl 6 · 2CH 3 COOC 2 H 5, MgTiCl 6 ·
_{6C 5 H 5 N, MgTiCl 5} (OCH 3) · 2CH 3 COOC 2 H 5, MgT
iCl ₅ N (C ₆ H ₅ ) ₂ .3CH ₃ COOC ₂ H ₅ , MgTiBr ₂ Cl _{4.
2 (C 2 H 5) 2} O, MnTiCl 5 · 4C 2 H 5 OH, Mg 3 V 2 Cl 12 ·
_{7CH 3 COOC 2 H 5, MgZrCl} 6 · 4 tetrahydrofuran. Other catalysts include other cobalt and iron catalysts well known Oite cationic catalysts such as AlCl _3, and in the art. See, for example, U.S. Patent Nos. 4,472,559 and 4
182,814.

Typically, these conventional transition metal catalyst compounds, except for some conventional chromium catalyst compounds, are activated by one or more of the conventional cocatalysts described below.

[0027]Conventional co-catalyst A conventional cocatalyst compound for the conventional transition metal catalyst compound described above has the formula M³M⁴ _vX ² _c R³ _bcWhere M³Is the IA of the Periodic Table of the Elements
, IIA, IIB, and IIIA; M⁴Is group IA of the periodic table of the elements
V is a number from 0 to 1; each X²Is halogen; c is 0
A number from 1 to 3; each R³Is a monovalent hydrocarbon group or hydrogen; b is 1 to
A number of 4; and bc is at least 1. Conventional transition metal catalyst as described above
Other conventional organometallic co-catalyst compounds for the compounds are of the formula M³R³ _kWhere
, M³Is lithium, sodium, beryllium, barium, boron, aluminum
Group IA, IIA, IIB, or IIIA, such as, zinc, cadmium, and gallium
K is M³Is 1, 2, or 3, depending on the valence of
Is usually M³Depends on the particular family to which R belongs;³Is any monovalent carbonized
It may be a hydrogen group.

Non-limiting examples of conventional organometallic co-catalyst compounds of Groups IA, IIA, and IIIA useful with respect to the conventional catalyst compounds described above include methyllithium, butyllithium, dihexylmercury, butylmagnesium, diethylcadmium. Benzyl potassium, diethyl zinc, tri-n-butyl aluminum, diisobutyl ethyl boron, diethyl cadmium, di-n-butyl zinc, and tri-n-amyl boron, and in particular, tri-hexyl-aluminum, triethyl aluminum , Trimethylaluminum, and alkylaluminums such as tri-isobutylaluminum. Other conventional cocatalyst compounds include mono-organic halides and hydrides of Group IIA metals, and mono- or di-organic halides and hydrides of Group IIIA metals. Non-limiting examples of such conventional co-catalyst compounds include di-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesium chloride, ethyl beryllium chloride, ethyl calcium bromide, di-isobutylaluminum hydride, methylaluminum hydride, diethylboron Includes hydride, hexyl beryllium hydride, dipropyl boron hydride, octyl magnesium hydride, butyl zinc hydride, dichloro boron hydride, di-bromo-aluminum hydride, and bromocadmium hydride. Conventional organometallic cocatalyst compounds are known to those skilled in the art, and a more complete discussion of these compounds is provided in US Pat.
21,002 and 5,093,415, which are fully incorporated herein by reference.

For the purposes of this patent specification and the appended claims, conventional transition metal catalyst compounds exclude the bulky ligand metallocene-type catalyst compounds discussed below. For the purposes of this patent specification and the appended claims, the term "promoter" means a conventional cocatalyst or a conventional organometallic cocatalyst compound. Bulk ligand metallocene-type catalyst compounds and catalyst systems for use in combination with the carbonyl compounds of the present invention are described below.

Bulky Ligand Metallocene-Type Catalyst Compounds In general, bulky ligand metallocene-type catalyst compounds are semi-sandwiches having one or more bulky ligands bonded to at least one metal atom. And fully sandwich type compounds. A typical bulky ligand metallocene compound is
Generally, one or more bulky ligands bound to at least one metal atom and 1
It is described as containing one or more leaving groups. As used herein and in the appended claims, the term "leaving group" is used to form a bulky ligand metallocene-type catalytic cation capable of polymerizing one or more olefins. It is a ligand that can be extracted from a metallocene-type catalyst compound of a different ligand.

Bulk ligands are generally represented by one or more open or fused rings (one or more) or ring systems (one or more) or a combination thereof. These rings (one or more) or ring systems (one or more) are typically composed of atoms selected from Groups 13-16, preferably these atoms are carbon, nitrogen, oxygen, It is selected from the group consisting of silicon, sulfur, phosphorus, boron, and aluminum or combinations thereof. Most preferably, the ring (s) or ring system (s) is a cyclopentadienyl ligand or cyclopentadienyl-type ligand structure or a pentadiene, cyclooctatetraenediyl or imide ligand. Like (but not limited to) other similar functionalized ligand structures such as ligands, they are composed of carbon atoms. The metal atoms are preferably selected from groups 3 to 16 of the periodic table of the elements and from the lanthanide or actinide series. Preferably the metal is fourth
To 12 and more preferably a transition metal from Groups 4, 5, and 6, and most preferably from Group 4.

[0032] In one embodiment, the metallocene-type catalyst compounds of the bulky ligands of the present invention have the formula: ^L A ^L is represented by B _MQ n (I), wherein, M is color of the Periodic Table of the Elements And may be from the metals of Groups 3 to 12 of the Periodic Table of the Elements or from the lanthanide or actinide series, preferably M is a Group 4, 5, or 6 transition metal, more preferably M is a Group 4 transition metal, more preferably M is zirconium, hafnium,
Or titanium.

[0033] L ^A and L ^B bulky ligands were either unsubstituted or substituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands, and substituted heteroatom / Or an open or fused ring (one or more) or ring system (one or more), such as a heteroatom-containing cyclopentadienyl-type ligand. Non-limiting examples of bulky ligands include cyclopentadienyl ligand, indenyl ligand, benzindenyl ligand, fluorenyl ligand, octahydrofluorenyl ligand, cyclooctatetraenediyl Ligand, azenyl ligand, azulene
e) ligand, pentalene ligand, phosphoyl (phos)
phoyl) ligand, pyrrolyl ligand, pyrazolyl (py
rozolyl ligands, carbazolyl ligands, borabenzene ligands and the like (including, for example, their hydrogenated variants such as tetrahydroindenyl ligands). In one embodiment, L ^A and L ^B may be any other ligand structure capable of eta-5 bound to M. In another embodiment, L ^A and L ^B are open, or preferably fused, ring or ring system, for example, hetero - in order to form a cyclopentadienyl ancillary ligand, in combination with the carbon atom, 1 One or more heteroatoms, such as nitrogen, silicon,
It can include boron, germanium, sulfur, and phosphorus. Other ^{L A} and ^{L B} bulky ligands, bulky, amides, phosphides, alkoxides, aryloxides, imides, Karuborido, Bororido, porphyrins, phthalocyanines, choline, and including other Poriazomakuro ring (polyazomacrocycles), these However, the present invention is not limited to this. Independently, each L ^A and L ^B may be the same or different types of bulky ligands bonded to M. In one embodiment, only one of ^{L A} or ^{L B} is present in formula (I).

[0034] Independently, each L ^A and L ^B may be replaced by a combination of good or substituent R in unsubstituted. Non-limiting examples of substituents R are hydrogen, or linear, branched,
Including one or more from the group selected from cyclic alkyl groups, or alkenyl, alkynyl, or aryl groups, or combinations thereof. In a preferred embodiment,
The substituent R has up to 50 non-hydrogen atoms, preferably 1 to 30 carbon atoms, which may also be substituted by halogen or heteroatoms or analogues.
Non-limiting examples of alkyl-substituted R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups (eg, all of their isomers such as tert-butyl, isopropyl, etc.). Including). Other hydrocarbyl groups include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl-substituted organic metalloid groups, such as trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like; and halocarbyl-substituted organic metalloid groups For example, tris (trifluoromethyl) -silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like; and a disubstituted boron group, for example, dimethylboron; and a disubstituted pnictogen group, for example, dimethylamine, dimethylphosphine , Diphenylamine, methylphenylphosphine, chalcogen groups, such as methoxy, ethoxy, propoxy, phenoxy, methyl sulfide, and ethyl sulfide. The non-hydrogen substituent R may include a plurality of atoms of carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium and the like (for example, but-3
-Olefins, such as, but not limited to, olefinically unsaturated substituents containing vinyl-terminated ligands such as -enyl, prop-2-enyl, hex-5-enyl. Also, at least two R groups, preferably at least two adjacent R groups, together form 3 to 4 selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or a combination thereof. A ring structure having 30 atoms is formed. Also, a substituent R such as 1-butanyl may form a carbon sigma bond to the metal M.

Other ligands, such as at least one leaving group Q, may be bound to the metal M. In one embodiment, Q is a monoanionic labile ligand having a sigma bond to M. Depending on the oxidation state of the metal, the value for n is 0, 1 such that formula (I) above represents a neutral bulky ligand metallocene-type catalyst compound.
Or 2.

Non-limiting examples of Q ligands include amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl groups, hydrides, having 1 to 20 carbon atoms.
Or a weak base, such as halogen or a combination thereof. In another embodiment, two or more Qs may form part of a fused ring or ring system. Other examples of Q ligands include substituents for R as described above, and cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyloxy, etoxy, propoxy, phenoxy, bis (N-methylanilide), dimethylamide, dimethylphosphide group and the like.

In one embodiment, the bulky ligand metallocene-type catalyst compound of the present invention comprises L ^A And L^BInclude compounds of formula I which are cross-linked to one another by a bridging group A.
These cross-linked compounds are used for the metallocene-type catalysis of cross-linked, bulky ligands.
Known as compound. Non-limiting examples of bridging group A include at least one
Containing at least one group 16 atom and often at least one carbon, oxygen, nitrogen, silicon, boron
Such as elemental, germanium, and tin atoms or combinations thereof (but not
(It is not limited thereto.) Preferred crosslinking groups A are carbon
, Silicon or germanium atoms, most preferably A is at least one silicon
It contains an elemental atom or at least one carbon atom. The crosslinking group A also contains a halogen.
It may also contain the substituent R defined above.

In another embodiment, the bulky ligand metallocene-type catalyst compound of the present invention has the formula: (C ₅ H _4-d R _d ) A _x (C ₅ H _4-d R _d ) M _g represented by _-2 (II), wherein, M is a group 4, 5, 6 transition _{metal, (C 5 H 4-d} R d) is bound to M, unsubstituted or substituted A cyclopentadienyl ligand or a bulky ligand of the cyclopentadienyl type, wherein each R is the same or different and is hydrogen or a substitution comprising up to 50 non-hydrogen atoms. A substituted or unsubstituted hydrocarbyl having 1 to 30 carbon atoms or a combination thereof, or two or more carbon atoms taken together to form 4
To 30 amino form part of the ring or ring system that is not been substituted or unsubstituted carbon atoms, A is a bridging the two _{(C 5 H 4-d R} d) rings, carbon, germanium , Boron, silicon, tin, phosphorus, or a group containing one or more of nitrogen atoms; more specifically, non-limiting examples of bridging group A include R ′ ₂ C, R ′ ₂ Si,
_{R '2 SiR' 2 Si,} R '2 SiR' 2 C, R '2 Ge, R' 2 SiR '2 G
_{e, R '2 GeR' 2} C, R'N, R'P, R '2 CR'N, R' 2 CR'P,
R ′ ₂ SiR′N, R ′ ₂ SiR′P, R ′ ₂ GeR′N, R ′ ₂ GeR′P, wherein R ′ is independently hydride, hydrocarbyl,
A group that is a substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organic metalloid, halocarbyl-substituted organic metalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen, or halogen, or two or more R's together. And independently forming a ring or ring system; and independently, each Q can be the same or different and is a hydride, substituted or substituted having 1 to 30 carbon atoms. No linear, cyclic, or branched hydrocarbyl, halogen, alkoxide, aryloxide, amide, phosphide, or other monovalent anionic ligand or a combination thereof; Together with the alkylidene ligand or the cyclic metallated hydrocarbyl ligand or other two
May form a divalent anionic chelating ligand, where g is an integer corresponding to the formal oxidation state of M, and d is selected from 0, 1, 2, 3, or 4 X is an integer of 0 to 1;

In one embodiment, the bulky ligand metallocene-type catalyst compound has the formula (I)
And bulky ligand L of (II)^A, L^B, (C₅H_4-dR_d)), Each R substituent is
Substituted with the same or different numbers of substituents on various bulky ligands
It is. In another embodiment, the bulky ligands L of formulas (I) and (II)^A, L ^B , (C₅H_4-dR_d) Are different from each other.

Other bulky ligand metallocene-type catalyst compounds useful in the present invention include bridged heteroatoms, mono-bulky ligand metallocene-type compounds. These types of catalysts and catalyst systems are described, for example, in PCT publication WO 92/00
333, WO94 / 07929, WO91 / 04257, WO94 / 03506
WO 96/00244 and WO 97/15602, U.S. Pat. No. 5,057,4.
No. 75, 5,096,867, 5,055,438, 5,198,4
Nos. 01, 5,227,440 and 5,264,405 and EP-A-0 420 436, all of which are fully incorporated herein by reference. It is described in. Other bulky ligand metallocene-type catalyst compounds and catalyst systems useful in the present invention are described in US Pat. No. 5,064,
No. 802, 5,145,819, 5,149,819, 5,243
No. 001, 5,239,022, 5,276,208, 5,296,
No. 434, No. 5,321,106, No. 5,329,031, No. 5,304,
No. 614, 5,677,401, 5,723,398, and 5,75
No. 3,578, and PCT International Publication Pamphlet WO93 / 08221, WO9
3/08199, WO 95/07140, WO 98/11144, and European Patent Publications EP-A-0 578 838, EP-A-0 638 595, EP-B
−0 513 380, EP-A1-0 816 372, EP-A2-0 8
39 834, and those described in EP-B1-0 632 819, all of which are fully incorporated herein by reference.

[0041] In another embodiment, the metallocene-type catalyst compounds of the bulky ligands of the formula: represented by ^L C AJMQ _n (III), wherein, M is the third to group 16 of the periodic table of the elements A metal atom or a metal selected from the group of actinides and lanthanides, preferably M is a Group 4-12 transition metal, and more preferably M is a Group 4, 5, or 6 transition metal; and Most preferably, M is a Group 4 transition metal in any oxidation state, especially titanium; L ^C is a substituted or unsubstituted bulky ligand attached to M; A is linked to M and J; J is a heteroatom ancillary ligand; and A is a bridging group; Q is a monovalent anionic ligand And n is an integer of 0, 1, or 2. In the above formula (III), L ^C , A and J form a fused ring system. In one embodiment, the formula (
L ^{C in} III) is as defined above for L ^A in formula (I);
A), M and Q in II) are as defined above in formula (I).

In another embodiment of the present invention, the bulky ligand meta useful in the present invention
The rocene-type catalyst compound has the formula: (C₅H_5-y-xR_x) (A_y) (JR '_z-1-y) M (Q)_n(L ') _w Wherein M is a transition metal from Group 4 in any oxidation state;
Preferably titanium, zirconium or hafnium, most preferably
It is titanium in an oxidation state of +2, +3, or +4. Represented by formula (IV)
Combinations of such compounds with transition metals of different oxidation states are also contemplated. L^CIs
, (C₅H_5-y-xR_x) And is a bulky ligand described above
. More specifically, (C₅H_5-y-xR_x) Is substituted with 0 to 5 substituents R.
A cyclopentadienyl ring or cyclopentadienyl type ring or ring system,
And x is 0, 1, 2, 3, or 4, representing the degree of substitution. Each R is German
A group selected from the group consisting of 1 to 30 non-hydrogen atoms. More details
Specifically, R is a hydrocarbyl group having 1 to 30 carbon atoms or a substituted
A hydrocarbyl group or a hydrocarbyl-substituted metalloid group,
Is a Group 14 or 15 element, preferably silicon or nitrogen or a combination thereof.
Certain, and halogen groups and combinations thereof. The substituent R is also
Silyl, germyl, amine, and hydrocarbyloxy groups, and mixtures thereof
including. Also, in another aspect, (C₅H_5-y-xR_x) Is two
The R group, preferably two adjacent R groups, together form 3 to 50 atoms,
Cyclo, preferably forming a ring or ring system having 3 to 30 carbon atoms
It is a pentadienyl ligand. This ring system, like the bulky ligands described above,
For example, indenyl, tetrahydroindenyl, fluorenyl, or octahydrofuran
Saturated or unsaturated polycyclic cyclopentadienyl-type ligands such as fluorenyl
Can be formed.

(JR ′ _z-1-y ) of formula (IV) is a heteroatom-containing ligand, wherein J is an element having a coordination number of 3 from group 15 of the periodic table of the element or It is an element from Group 16 having a coordination number of 2. Preferably, J is a nitrogen, phosphorus, oxygen, or sulfur atom, with nitrogen being most preferred. Each R ′ is independently a group selected from the group consisting of a hydrocarbyl group having 1 to 20 carbon atoms, or as defined for R in formula (I) above. y is 0 or 1, and z is the coordination number of the element J. In one embodiment, in formula (IV),
III) J is represented by ( _JR'z-1-y ).

In Formula (IV), each Q is independently halogen, hydride, or substituted or unsubstituted hydrocarbyl, alkoxide, aryloxide, sulfide, silyl having 1 to 30 carbon atoms. , Amides, or phosphides. Q can also include a hydrocarbyl group having ethylenic unsaturation, thereby forming an η ³ bond to M. The two Qs may also be alkylidene, cyclic metallated hydrocarbyl, or other divalent anionic chelating ligand. The integer n is 0
1, 2, or 3.

A in the formula (IV) is an element of Groups 13 to 16, preferably an element of Groups 14 and 15,
Most preferably, it is a covalent cross-linking group containing a Group 14 element. Non-limiting examples of bridging groups A include dialkyl, alkylaryl, or diaryl silicon or germanium groups, alkyl or aryl phosphine or amine groups, or hydrocarbyl groups such as methylene, ethylene, and the like.

Optionally associated with formula (IV) is L ′, ie a Lewis base such as diethyl ether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine and the like; And w is a number from 0 to 3. Further, L ′ may be linked to any of R, R ′, or Q, and n is 0, 1, 2, or 3.

In another embodiment, the bulky ligand metallocene-type catalyst compounds are disclosed in US Pat. Nos. 5,527,752 and 5,747,406 and EP-B1-07.
Metal, preferably a transition metal, a bulky ligand, preferably substituted or substituted, such as those described in US Pat. A pi-bonded ligand which is not
A complex consisting of one or more heteroallyl moieties.

[0048] In one embodiment, the metallocene-type catalyst compounds of the bulky ligands of the formula: represented by ^{_{L D MQ 2 (YZ) A}} n (V), wherein, M is a Group 3 to 16 metal , and the preferably 4 to 12 transition metal, and most preferably be in the 4, 5, or 6 transition metal; is L ^D, not bound to have been replaced or substituted in M Are bulky ligands; each Q is independently linked to M, and Q ₂ (YZ) has a charge of 1
Forming a unicharged polydentate ligand of
A or Q is a monovalent anionic ligand also bonded to M; n is 1 or 2.

In another embodiment, M is a Group 4, 5, or 6 transition metal, preferably from Group 4, more preferably titanium, zirconium, and hafnium, and most preferably Preferably zirconium; L ^D is selected from the group of bulky ligands consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenediyl, and It includes a bulky ligand as described above for ^{L a} of formula (I); Q is, -O -, - NR -, - CR 2 -, and is selected from the group consisting of -S-; Y is C Or S; Z is —OR, —NR ₂ , —CR ₃ ,
_{-SR, -SiR 3, -PR 2,} -H, and it is selected from the group consisting of substituted or unsubstituted aryl group, provided that when Q is -NR-, Z is -
_{OR, -NR 2, -SR, -SiR} 3, selected from the group consisting of -PR _2, and -H; R is selected from the group comprising carbon, silicon, nitrogen, oxygen, and / or phosphorus, preferably R is a hydrocarbon group containing 1 to 20 carbon atoms, most preferably an alkyl, cycloalkyl or aryl group; n is an integer from 1 to 4, preferably 1 or 2; A is a monovalent anionic group when n is 2,
Or, A is a divalent anionic group when n is 1; preferably A is a carbamate, carboxylate, or other heteroallyl moiety represented by the combination of Q, Y, and Z. In formula (V) Another embodiment, optionally, _{T m} is a bridging group bonded to the another ^{L D} of ^{L D} and one other ^L D _MQ 2 YZA _n compound, where m is an integer from 2 to 7, preferably from 2 to 6, most preferably 2 or 3; and T is an alkylene and arylene group having 1 to 10 carbon atoms (optionally a carbon or heteroatom (1 that's all),
(Substituted with germanium, silicon and alkylphosphine).

In another embodiment of the present invention, the bulky ligand metallocene catalyst compound is a heterocyclic ligand complex, wherein the bulky ligand is one or more rings or rings. The system (one or more) is one that contains one or more heteroatoms or a combination thereof. Non-limiting examples of heteroatoms are Group 13-16 elements, preferably including nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus, and tin. Examples of metallocene type catalyst compounds of these bulky ligands are described in WO96 / 33202, WO96 / 3.
4021, WO97 / 17379, and WO98 / 22486, and U.S. Patent Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233. No., 049, and 5,744,417, all of which are incorporated herein by reference.

In another embodiment, the bulky ligand metallocene-type catalyst compound is 199
Such as those described in U.S. Patent Application Serial No. 09 / 103,620, filed June 23, 08, which is incorporated herein by reference.
Complexes known as transition metal catalysts based on bidentate ligands containing a pyridine or quinoline moiety.

In one embodiment, the bulky ligand metallocene-type catalyst compound is represented by the formula: ((Z) XA _t (YJ)) _q MQ _n (VI), wherein M is an element of the element A metal selected from Groups 3 to 13 of the periodic table or the lanthanide and actinide series; Q is bonded to M, and each Q is 1
X and Y are bound to M; 1 of X and Y
One or more are heteroatoms, preferably both X and Y are heteroatoms;
Is contained in a heterocyclic ring J, wherein J contains 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z is bonded to X, wherein Z is Containing from 1 to 50 non-hydrogen atoms, preferably 1 to 50 carbon atoms, preferably
Z is a cyclic group containing 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is X, Y or J Is a bridging group bonded to at least one, preferably X and J; q is 1 or 2; n
Is an integer of 1 to 4 depending on the oxidation state of M. In one embodiment, when X is oxygen or sulfur, Z is optional. In another embodiment, when X is nitrogen or phosphorus, Z is present. In one embodiment, Z is preferably an aryl group, more preferably a substituted aryl group.

In another embodiment, these metallocene-type catalyst compounds are represented by the formula: ((R ′ _m Z) XA _t (YJR ″ _m )) _q MQ _n (VII), wherein M is A metal selected from Groups 3 to 13 of the Periodic Table of the Elements, preferably a Group 4 to 12 transition metal, more preferably a Group 4, 5, or 6 transition metal, even more preferably titanium, zirconium, or Group 4 transition metals such as hafnium, and most preferably zirconium.

Each Q is attached to M, and each Q is a monovalent, divalent, or trivalent anion. Preferably, each Q is independently selected from the group consisting of halogen, hydrogen, alkyl having 1 to 20 carbon atoms, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrocarboxy, or phenoxy. You. Each Q may also be an amide, phosphide, sulfide, silylalkyl, diketonates, and carboxylate. If desired, each Q can include one or more heteroatoms, more preferably, each Q is selected from the group consisting of halide, alkyl, and arylalkyl groups. Most preferably, each Q is selected from the group consisting of an arylalkyl group such as benzyl.

X and Y are each preferably a heteroatom, more preferably independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, even more preferably nitrogen or phosphorus, and most preferably nitrogen It is.

Y is contained in a heterocyclic ring or ring system J. J contains 2 to 30 carbon atoms, preferably 2 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, and most preferably 5 carbon atoms. If desired, the heterocyclic ring J containing Y can contain additional heteroatoms. J is hydrogen, or linear, branched,
It may be substituted with a cyclic, alkyl, or R "group independently selected from the group consisting of an alkenyl, alkynyl, alkoxy, aryl, or aryloxy group. Together, they may form cyclic moieties such as aliphatic or aromatic rings. Preferably R "is hydrogen or an aryl group, most preferably R" is hydrogen. When R "is an aryl group and Y is nitrogen, a quinoline group is formed. If desired, R" may be conjugated to A.

Z is a hydrocarbyl group attached to X, preferably Z is a hydrocarbyl group of 1 to 50 carbon atoms, preferably Z is a cyclic group having 3 to 30 carbon atoms Preferably, Z is a substituted or unsubstituted cyclic group having 3 to 30 carbon atoms, optionally containing one or more heteroatoms, more preferably Z is an aryl group, Most preferably, Z is a substituted aryl group.

Z may be substituted with hydrogen or an R ′ group independently selected from the group consisting of a linear, branched, alkyl group, or a cyclic alkyl, alkenyl, alkynyl, or aryl group. Good. Also, two or more R's may together form a cyclic moiety, such as an aliphatic or aromatic ring. Preferably R 'is an alkyl group having 1 to 20 carbon atoms, more preferably R' is methyl, ethyl, propyl, butyl, pentyl and the like (including isomers thereof), more preferably R '
Is a secondary or tertiary hydrocarbon, such as isopropyl, t-butyl, and the like;
Most preferably, R 'is an isopropyl group. If desired, the R ′ group may be conjugated to A. Preferably, at least one R ′ is ortho to X.

When t is 1, A is a bridging group bonded to at least one, and preferably both, of X and J. The bridging group A comprises one or more thirteenth to sixteenth from the periodic table of the elements.
Including group elements. More preferably, A comprises one or more Group 14 elements, most preferably A is a substituted carbon group, a disubstituted carbon group, or a vinyl group.

In formula (VII), m is independently an integer from 0 to 5, preferably 2; n is an integer from 1 to 4, typically depending on the oxidation state of M ; And q
Is 1 or 2, and when q is 2, two ((R ′ _m Z) X of formula (VII)
A (YJR ″ _m )) are cross-linked to each other via a cross-linking group, preferably a cross-linking group containing a Group 14 element, and in a preferred embodiment represented by formula (VI) or (VII) The compound may be contacted with acetone.

Other Bulk Ligand Metallocene-Type Catalyst Compounds In one embodiment, the bulky ligand metallocene-type catalyst compound is Johns
on, et al., "New Pd (II)-and Ni (II) -Based."
Catalysts for Polymerization of Ethy
line and a-Olefins, "J. Am. Chem. So.
c. 1995, 117, 6414-6415, and Johnson et al.,
“Copolymerization of Ethylene and Pr
opilene with Functionalized Vinyl Mo
names by Palladium (II) Catalysts ",
J. Am. Chem. Soc. , 1996, 118, 267-26.
No. 8 and WO 96/23010 published August 1, 1996, all of which are incorporated herein by reference, include complexes of Ni ²⁺ and Pd ^2+. , Within the scope of the present invention. These complexes may be dialkyl ether adducts or alkylation reaction products of the described dihalide complexes which can be activated cationically by the activators of the invention described below.

Further included as bulky ligand metallocene-type catalyst compounds are PCT
International Publication Pamphlets WO96 / 23010 and WO97 / 48735 and Gi
bson et al., Chem. Comm. Pp. 849-850 (1998)
) (All of which are incorporated herein by reference) are diimine-based ligands of Group 8-10 metal compounds.

Other bulky ligand metallocene catalysts are described in EP-A2-0 816 38
No. 4 (which is incorporated herein by reference) are Group 5 and 6 metal imide complexes. In addition, the bulky ligand metallocene catalyst has a D
. H. Organometallics by McConville et al.
1195, 14, 5478-5480, which is incorporated herein by reference.
Group compounds.

In one embodiment, the bulky ligand metallocene-type catalysts of the present invention described above also include their structural or optical or enantiomers (meso and racemic isomers) and mixtures thereof. Is intended.

Activators and Activation Methods for Bulk Ligand Metallocene Catalyst Compounds The bulky ligand metallocene catalyst compounds having at least one fluoride leaving group or fluorine-containing leaving group include: Typically, the olefin is co-ordinated, intercalated, and activated in various ways to produce a catalytic compound having a vacant coordination site that polymerizes.

As used herein and in the appended claims, the term “activator” refers to a compound or component or method capable of activating the bulky ligand metallocene-type catalyst compounds of the invention described above. Is defined to be. Non-limiting activators include, for example, Lewis acids or non-coordinating ionic activators or ionizing activators or bulky ligands that are catalytically active with neutral bulky ligand metallocene-type catalyst compounds. Any other compound (including Lewis bases, alkylaluminums, conventional cocatalysts, and combinations thereof) that can be converted to a metallocene cation of Using alumoxane or modified alumoxane as activator and / or ionizing the metallocene-type catalyst compound of the neutral bulky ligand, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or It is also within the scope of the present invention to use a neutral or ionic, ionizing activator, such as a trisperfluorophenylboron metalloid precursor.

In one embodiment, an activation method using an ionized ionic activator that does not contain an active proton but is capable of producing both a bulky ligand metallocene-type catalytic cation and a non-coordinating anion. Are also intended, EP-A-0 426
637, EP-A-0 573 403, and U.S. Pat. No. 5,387,568, which are incorporated herein by reference.

There are various methods for producing alumoxanes and modified alumoxanes, non-limiting examples of which are described in US Pat. Nos. 4,665,208, 4,952,54
No. 0, 5,091,352, 5,206,199, 5,204,41
No. 9, No. 4,874,734, No. 4,924,018, No. 4,908,46
No. 3, 4,968,827, 5,308,815, 5,329,03
No. 2, No. 5,248,801, No. 5,235,081, No. 5,157,13
No. 7, No. 5,103,031, No. 5,391,793, No. 5,391,52
No. 9, No. 5,693, 838, No. 5,731,253, No. 5,731,45
No. 5,744,656, and EP-A-0 561 476
, EP-B1-0 279 586, and EP-A-0 594 218, and WO 94/10180, all of which are fully incorporated herein by reference.

The ionized compound can include an active proton, or can include certain other cations that associate with the remaining ions of the ionized compound but do not or only loosely coordinate. Such compounds and analogs are described in European Patent Publication EP
-A-0 570 982, EP-A-0 520 732, EP-A-0 495
375, EP-A-500 944, EP-A-0 277 003 and EP-A-0
277 004, and U.S. Patent Nos. 5,153,157, 5,198,40.
No. 1, No. 5,066,741, No. 5,206,197, No. 5,241,02
No. 5,384,299, and 5,502,124, and U.S. Patent Application Serial No. 08 / 285,380, filed August 3, 1994, all of which are incorporated herein by reference. It is fully incorporated herein by reference.

Other activators include those described in PCT International Publication WO 98/07515 such as tris (2,2 ′, 2 ″ -nonafluorobiphenyl) fluoroaluminate, Combinations of multiple activators, such as, for example, combined alumoxanes and ionizing activators, are also contemplated by the present invention and are fully incorporated herein by reference, for example, PCT International Publication WO94. See U.S. Patent No. 5,073,157 and WO 95/14044 and U.S. Patent Nos. 5,153,157 and 5,453,410, all of which are fully incorporated herein by reference. WO 98/09996, incorporated herein, discloses a bulky ligand metallocene-type catalyst compound. Loreto (perchlorates), Peruyodeto (p
and activation with iodates (including their hydrates). WO incorporated by reference
98/30602 and WO 98/30603 describe the use of lithium (2,2'-bisphenyl-ditrimethylsilicate) .4THF as an activator for bulky ligand metallocene-type catalyst compounds. Also, radiation (see EP-B1-0 615 981 which is incorporated herein by reference).
Activation methods, such as the use of electrochemical oxidation, may also be used to neutralize bulky ligand metallocene-type catalyst compounds or precursors to bulky ligand metallocene-type cations that can polymerize olefins. It is intended as an activation method for the purpose of

The bulky ligand metallocene-type catalyst compound is combined with one or more of the above-described activators or activation methods and one or more of the catalyst compounds represented by Formulas (I) through (VII). Combinations are also within the scope of the present invention.

It is further contemplated by the present invention that other catalysts may be combined with the bulky ligand metallocene-type catalyst compounds of the present invention. For example, U.S. Patent Nos. 4,937,299, 4,935,474, and 5,281,679.
No. 5,359,015, 5,470,811 and 5,719,2
See No. 41. All of which are fully incorporated herein by reference. US patent application Ser. No. 09/191, filed Nov. 13, 1998.
Any one of the bulky ligand metallocene-type catalyst compounds of the present invention having at least one fluoride or fluorine containing leaving group, such as described in U.S. Pat.

In another aspect of the present invention, one or more bulky ligand metallocene-type catalysts or catalyst systems can be used in combination with one or more conventional catalyst compounds or catalyst systems. Non-limiting examples of mixed catalysts and catalyst systems are described in US Pat.
No. 965, No. 4,325,837, No. 4,701,432, No. 5,124
No. 5,418, 5,077,255, No. 5,183,867, No. 5,391
No. 5,660, 5,395,810, 5,691,264, 5,723
399 and 5,767,031, and published August 1, 1996.
It is described in PCT International Publication WO 96/23010, all of which are fully incorporated herein by reference.

Loading Methods The bulky ligand metallocene-type catalyst compounds and catalyst systems described above can be prepared using one or more loading methods well known in the art or described below. It can be combined with a support material or carrier. In a preferred embodiment,
The process of the present invention uses a supported form of the polymerization catalyst. For example, in a most preferred embodiment, the bulky ligand metallocene-type catalyst compound or catalyst system is in a supported form, e.g., deposited on a support material or carrier, contacted with a support material or carrier, Or in a supported form, incorporated into a support material or carrier, adsorbed on or absorbed into a support material or carrier.

The terms “support” or “carrier” are used interchangeably and may be any support material, preferably a porous support material, for example, talc, inorganic oxides, and inorganic chlorides. It is. Other supports include resinous supports such as polystyrene, functionalized or crosslinked organic supports such as polystyrene divinylbenzene polyolefin or polymeric compounds, zeolites, clays, or other organic or inorganic support materials. Or a mixture thereof.

Preferred supports are inorganic oxides containing Group 2, 3, 4, 5, 13 or 14 metal oxides. Preferred supports include silica, alumina, silica-alumina, magnesium chloride, and mixtures thereof. Other useful supports are magnesia, titania, zirconia, montmorillonite (EP-B10 511 665).
). Also, combinations of these support materials, for example, silica-chromium, silica-alumina, silica-titania, and the like can be used.

The support, most preferably the inorganic oxide, has a surface area in the range of about 10 to about 700 m ² / g, a pore volume in the range of about 0.1 to about 4.0 cc / g.
and preferably an average particle size in the range of about 5 to about 500 μm. The support has a surface area in the range of about 50 to about 500 m ² / g and a pore volume of about 0 to about 500 m ² / g.
. 5 to about 3.5 cc / g and an average particle size of about 10 to about 20.
More preferably, it is within the range of 0 μm. The surface area of the carrier is from about 100 to about 400
m is in the range of ² / g, is in the pore volume in the range of from about 0.8 to about 3.0 cc / g, and average particle size is most preferably in the range of from about 5 to about 100 [mu] m. The average pore size of the carriers of the present invention is typically in the range of 10 to 1000 Angstroms, preferably in the range of 50 to about 500 Angstroms, and most preferably in the range of 75 to about 350 Angstroms. Is within.

Examples of loading bulky ligand metallocene catalyst systems of the present invention are described in US Pat.
No. 01,432, No. 4,808,561, No. 4,912,075, No. 4,9
No. 25,821, No. 4,937,217, No. 5,008,228, No. 5,2
No. 38,892, No. 5,240,894, No. 5,332,706, No. 5,3
No. 46,925, No. 5,422,325, No. 5,466,649, No. 5,4
Nos. 66,766, 5,468,702, 5,529,965, 5,5
Nos. 54,704, 5,629,253, 5,639,835, 5,6
No. 25,015, No. 5,643,847, No. 5,665,665, No. 5,6
Nos. 98,487, 5,714,424, 5,723,400, 5,7
No. 23,402, No. 5,731,261, No. 5,759,940, No. 5,7
Nos. 67,032 and 5,770,664, and U.S. Patent Application No. 271,598 filed July 7, 1994 and U.S. Patent Application No. 788,736 filed January 23, 1997. , And PCT International Publication Pamphlet WO95 /
32995, WO95 / 14044, WO96 / 06187, and WO97 / 0
2297, all of which are fully incorporated herein by reference.

In one embodiment, the bulky ligand metallocene-type catalyst compound of the invention can be deposited on the same or a separate support with the activator, or
It can be used in unsupported form, or deposited on a different support than the supported bulky ligand metallocene-type catalyst compounds of the present invention, or using any combination thereof. it can.

Various methods exist in the art for supporting the polymerization catalyst compound or catalyst system of the present invention. For example, the bulky ligand metallocene-type catalyst compounds of the present invention are disclosed in U.S. Patent Nos. 5,473,202 and 5,770,755, which are incorporated herein by reference. The bulky ligand metallocene-type catalyst systems of the present invention can include the polymer-bound ligands described.
648,310, which is incorporated herein by reference; may be spray dried; used with the bulky ligand metallocene-type catalyst systems of the present invention. The support described in EP-A-0 802 22
No. 03, which is functionalized as described in US Pat.
No. 88,880, which is incorporated herein by reference.

In a preferred embodiment, the present invention relates to PCT International Publication WO96 / 1
A supported, including an antistatic or surface modifier used during the preparation of a supported catalyst system, as described in 1960, which is incorporated herein by reference. Provided is a bulky ligand metallocene catalyst system. The catalyst system of the present invention can be prepared in the presence of an olefin, for example, hexene-1.

A preferred method for preparing the supported bulky ligand metallocene-type catalyst systems of the present invention is described below and is described in US Patent Application No. 265,533, filed June 24, 1994. And 265, 532, and PCT International Publication Pamphlets WO96 / 00245 and WO96 / 245, both published on January 4, 1996.
00243, all of which are fully incorporated herein by reference. In this preferred embodiment, the bulky ligand metallocene-type catalyst compound is slurried in a liquid to form a metallocene solution, and a separate solution containing the activator and the liquid is formed. The liquid may be any compatible solvent or other liquid capable of forming a solution or analog with the bulky ligand metallocene-type catalyst compound and / or activator of the present invention. In a most preferred embodiment, the liquid may be a cycloaliphatic or aromatic hydrocarbon, most preferably toluene. The total volume of the solution of the bulky ligand metallocene-type catalyst compound and the activator or the total volume of the solution of the bulky ligand metallocene-type catalyst compound and the activator is the pore volume of the porous support. A solution of the bulky ligand metallocene-type catalyst compound and a solution of the activator are mixed together so as to be less than 4 times, more preferably less than 3 times, and still more preferably less than 2 times, to form a porous support. Either added or a porous support is added to these solutions, but the preferred range is 1.1 to 3.5 times, most preferably 1 to 3.5 times.
. It is in the range of 2 to 3 times.

[0083] Methods for measuring the total pore volume of a porous support are known in the art.
Details of one of these methods can be found in Volume 1, Experimental.
Methods in Catalytic Research (Acad
emic Press, 1968) (see especially pages 67-96). This preferred method involves the use of a traditional BET device for nitrogen adsorption. Another method known in the art is described in Innes,
Total porosity and Particle Density
of Fluid Catalysts By Liquid Tititi
on, Vol. 28, No. 3, Analytical Chemi
STRY 332-334 (March 1956).

The molar ratio of the metal-supported bulky ligand of the activator component to the metal of the metallocene-type catalyst compound is from 0.3: 1 to 1000: 1, preferably from 20: 1 to 80.
0: 1, and most preferably in the range of 50: 1 to 500: 1. When the activator is an ionizing activator, such as one based on the anionic tetrakis (pentafluorophenyl) boron, the molar ratio of the bulky ligand of the metal of the activator component to the metal component of the metallocene catalyst is 0.3. Preferably, it is in the range of 1: 1 to 3: 1. When an unsupported bulky metallocene catalyst system is used, the molar ratio of the bulky ligand metal to the metallocene catalyst compound of the activator component to the metal is 0.
. It is in the range of 3: 1 to 10,000: 1, preferably 100: 1 to 5000: 1, and most preferably 500: 1 to 2000: 1.

In one aspect of the invention, one or more olefins, preferably one or more olefins
C ₂ to olefins or alpha C ₃₀ - olefins, preferably ethylene or propylene or combinations thereof, prior to the main polymerization, preliminary polymerization in the presence of a metallocene catalyst system of the bulky ligands of the present invention . The prepolymerization can be performed batchwise or continuously in a gas phase, solution phase, or slurry phase, including high pressure. The prepolymerization can be performed with any olefin monomers or combinations thereof and / or in the presence of any molecular weight regulator such as hydrogen. For examples of prepolymerization procedures, see U.S. Patent Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, and 5,283,278. And 5,705,578, and EP-B-0279 863,
And PCT publication WO 97/44371. All of which are fully incorporated herein by reference.

[0086] In one embodiment, the polymerization catalyst is in unsupported form, preferably in US Pat.
Nos. 317,036 and 5,693,727 and European Patent Publication EP-A-0.
593 083, all of which are used herein in liquid form as described herein. The polymerization catalyst in liquid form is P
The reactor can be fed as described in CT International Publication WO 97/46599, which is fully incorporated by reference.

Carbonyl Compounds Carbonyl compounds are well known in the art. In this specification and the appended claims, a carbonyl compound is an organic carbonyl compound having the general formula: R (C = O) _nR '(A), wherein n is 1 or 2, preferably N is 2 and R and R ′ may be the same or different and may have up to 100 non-hydrogen atoms, preferably 1 to 50 carbon atoms, optionally substituted by heteroatoms or substituents. It can have atoms. R and R ′ can be branched or unbranched, saturated or unsaturated, aliphatic or cycloaliphatic or aromatic groups or mixtures of aliphatic or aromatic groups. In one aspect, more than one carbonyl group is present in the same molecule. Non-limiting examples of these diketones include aromatic diketones where n is 2 in formula (A) above.

In one embodiment, when R or R ′ is a hydrogen atom, the resulting compound is an aldehyde, and when R or R ′ is an —OH group, the resulting compound is a carboxylic acid, or When R or R 'is -OR "and R" is defined as having 1 to 50 carbon atoms, the resulting compound is a carboxylic ester.

Non-limiting examples include acetone, acetophenone, methyl octyl ketone, benzophenone, 9-fluorenone, 2-3 butanedione, benzyl
, Including acetaldehyde, decane aldehyde and benzaldehyde, acetic acid, decanoic acid, benzoic acid, methyl acetate, decyl acetate, phenyl acetate, methyl decanoate, decyl decanoate, phenyl decanoate, methyl benzoate, decyl benzoate, phenyl benzoate However, the present invention is not limited to these.

[0090] Non-limiting commercially available carbonyl compounds, such as benzyl and the like, are available from Aldrich, Milwaukee, WI. Other carbonyl compounds include the fluorinated benzyls described in US Pat. No. 5,463,135, which is incorporated herein by reference. In one embodiment, the carbonyl compounds of the present invention are disclosed in U.S. Pat.
No. 110,184 (both of which are incorporated herein by reference) including diaryl ketones and α-diketones. Non-limiting examples are fluorenone, anthrone, xanthon (xant)
hone), thioxanthone, phenanthrenequinone, biacetyl (biace)
tyl), camphorquinine, and acenaphthacene.

The most preferred carbonyl compound is a diaryl ketone, preferably diphenyldiketone, most particularly benzyl.

[0092] In one embodiment, the carbonyl compounds of the present invention have a melting point above 50 ° C, most preferably above 80 ° C. Non-limiting examples of carbonyl compounds having a melting point above 80 ° C include benzyl, 9-fluorinone (9-fluorinone).
one), and 2-carboxybenzaldehyde.

[0093] In one aspect of the invention, more than one carbonyl compound is used.

[0094] In one embodiment, the carbonyl compound is a fatty amine, such as chemamine (K
emamine) AS 990/2 zinc additive (blend of ethoxylated stearylamine and zinc stearate) or chemamine AS 990/3 (ethoxylated stearylamine, zinc stearate, and octadecyl-3,5-di-te)
rt-butyl-4-hydroxyhydrocinnamate). Both of these blends are available from Witco Corporation of Memphis, TN. In another embodiment, the carbonyl compound is a carboxylate salt of a metal ester, for example, aluminum mono, di- as described in US patent application Ser. No. 09 / 113,216 filed Jul. 10, 1998. And aluminum carboxylate, such as tri-stearate, aluminum octoate, oleate, and cyclohexyl butyrate.

Methods for Preparing Catalyst Compositions Methods for preparing catalyst compositions generally involve combining, contacting, blending, and / or mixing a catalyst system or polymerization catalyst with a carbonyl compound.

In one embodiment of the method of the present invention, the conventional transition metal catalyst and / or the bulky ligand metallocene catalyst is combined, contacted or blended with at least one carbonyl compound. And / or mixed. In a most preferred embodiment, the conventional transition metal catalyst and / or the bulky ligand metallocene catalyst is supported on a support.

In another embodiment, the steps of the method of the present invention comprise forming a polymerization catalyst,
Preferably, comprising forming a supported polymerization catalyst and contacting the polymerization catalyst with at least one carbonyl compound. In a preferred method, the polymerization catalyst comprises a catalyst compound, activator or cocatalyst and a carrier, preferably the polymerization catalyst is a supported bulky ligand metallocene-type catalyst.

Those skilled in the art will recognize that depending on the catalyst system and carbonyl compound used, certain conditions of temperature and pressure are required, for example, to prevent loss of activity of the catalyst system.

In one embodiment of the process of the present invention, the carbonyl compound is combined with a catalyst system, preferably a supported catalyst system, most preferably a supported bulky ligand metallocene-type catalyst system at ambient temperature and pressure. Contacted. Preferably, the contact temperature for combining the polymerization catalyst with the carbonyl compound is in the range of 0 ° C to about 100 ° C, more preferably 15 ° C to about 75 ° C, and most preferably about ambient temperature and pressure. .

In a preferred embodiment, the contact between the polymerization catalyst and the carbonyl compound is performed under an atmosphere of an inert gas such as nitrogen. However, it is also contemplated that the combination of the polymerization catalyst and the carbonyl compound can be performed in the presence of olefin (s), solvent, hydrogen and the like.

In one embodiment, the carbonyl compound can be added at any stage during the preparation of the polymerization catalyst.

In one embodiment of the method of the present invention, the polymerization catalyst and the carbonyl compound are combined in the presence of a liquid, for example, the liquid may be mineral oil, toluene, hexane, isobutane, or a mixture thereof. In a more preferred method, the carbonyl compound is combined with a polymerization catalyst formed in a liquid, preferably in a slurry, or combined with a substantially dry or dried polymerization catalyst reslurried in a liquid. It is.

In one embodiment, the contact time of the carbonyl compound with the polymerization catalyst depends on one or more of the conditions: temperature and pressure, type of mixing equipment, amount of components to be combined, and also the polymerization catalyst / carbonyl compound combination. Depending on the mechanism for introducing the reactor into the reactor.

Preferably, the polymerization catalyst, preferably a bulky ligand metallocene-type catalyst compound and the support, comprises the carbonyl compound and the carbonyl compound for a period of time greater than 1 second, preferably from about 1 minute to about 4 minutes.
8 hours, more preferably about 10 minutes to about 10 hours, and most preferably about 30 minutes.
The contact is made for minutes to about 6 hours. The time of contact means only the mixing time.

In one embodiment, the ratio of the weight of the carbonyl compound to the weight of the transition metal of the catalyst compound is in the range of about 0.01 to about 1000% by weight, preferably in the range of 1 to about 100. , More preferably in the range of about 2 to about 50, and most preferably in the range of about 4 to about 20. In one embodiment,
The ratio of the weight of the carbonyl compound to the weight of the transition metal of the catalyst compound is in the range of about 2 to about 20, more preferably in the range of about 2 to about 12, and most preferably about 4 to about 10%. Within the range.

In another embodiment of the process of the present invention, the weight percentage of carbonyl compound based on the total weight of the polymerization catalyst is in the range from about 0.5% to about 500% by weight, preferably 1% by weight. To about 25% by weight, more preferably about 2% by weight.
%, And most preferably in the range of about 2% to about 10% by weight. In another embodiment, the weight percent of carbonyl compound based on the total weight of the polymerization catalyst is in the range of 1 to about 50% by weight, preferably in the range of 2% to about 30% by weight, and most Preferably it is in the range of about 2% to about 20% by weight.

[0107] Mixing techniques and devices intended for use in the methods of the present invention are well known. Mixing techniques can include mechanical mixing means, such as shaking, stirring, tumbling, and rolling. Another technique that is contemplated includes the use of fluidization, for example, in a fluidized bed reactor where the circulating gas provides mixing. Non-limiting examples of mixing devices for combining the solid polymerization catalyst and the solid carbonyl compound in the most preferred embodiment include ribbon blenders, static mixers, double cone blenders, drum tumblers, drum rollers, dehydrators, fluidized beds, helical mixers , And a conical screw mixer.

In one embodiment of the process of the invention, the supported conventional transition metal catalyst, preferably a supported bulky ligand metallocene-type catalyst, comprises a carbonyl compound and a substantial portion of the supported catalyst The tumbling is such that the compound is intimately mixed and / or substantially contacted with the compound.

In a preferred embodiment of the present invention, the catalyst system of the present invention is supported on a support, preferably the supported catalyst system is substantially dry, preformed or substantially dry. And / or fluent. In a particularly preferred method of the invention, the preformed supported catalyst system is contacted with at least one carbonyl compound. The carbonyl compound may be in solution or slurry or in a dry state, preferably the carbonyl compound is substantially dry or in a dry state. In a most preferred embodiment, the carbonyl compound is contacted with a supported catalyst system, preferably a supported bulky ligand metallocene type catalyst system, in a rotary mixer under a nitrogen atmosphere, most preferably the mixer is a tumble mixer. Or in a fluidized bed mixing process, in which the polymerization catalyst and the carbonyl compound are in the solid state, ie, they are both substantially dry or in a dry state.

In one embodiment of the method of the present invention, a conventional transition metal catalyst compound, preferably a bulky ligand metallocene type catalyst compound, is contacted with a support to form a supported catalyst compound. . In this method, the activator or cocatalyst for the catalyst compound is contacted with a separate support to form a supported activator or supported cocatalyst. In this particular aspect of the invention, the carbonyl compound is then mixed with the supported catalyst compound or supported activator or cocatalyst, mixed separately in any order, simultaneously mixed, or separately supported. It is also contemplated that prior to mixing the supported catalyst with the activator or cocatalyst, it is mixed with only one of the supported catalyst or (preferably) the supported activator.

In another embodiment, the polymerization catalyst / carbonyl compound can be contacted with a liquid, such as mineral oil, and introduced to the polymerization process in a slurry state. In this particular embodiment, the polymerization catalyst is preferably a supported polymerization catalyst.

In one embodiment, the method of the present invention co-injects an unsupported polymerization catalyst and a carbonyl compound into a reactor. In one embodiment, the polymerization catalyst is in unsupported form, preferably in US Pat. Nos. 5,317,036 and 5,693,72.
7, and in liquid form as described in European Patent Application EP-A-0 593 083, all of which are incorporated herein by reference. The polymerization catalyst in liquid form is disclosed in PCT International Publication Pamphlet WO97 /
46599, which can be fed to the reactor with the carbonyl compound using the injection method described in US Pat.

If a combination of a carbonyl compound and a metallocene catalyst system of an unsupported bulky ligand is used, the molar ratio of the bulky ligand of the activator component to the metal of the metallocene catalyst compound of the activator component is , 0.3: 1 to 10,000: 1, preferably 100: 1 to 5000: 1, and most preferably 500: 1.
: 1 to 2000: 1.

In one embodiment, the polymerization catalyst and / or catalyst composition, polymerization catalyst and carbonyl compound have a productivity of greater than 1500 g of polymer / g of catalyst, preferably greater than 2000 g of polymer / g of catalyst, more preferably Has a productivity greater than 2500 g polymer per gram of catalyst, and most preferably greater than 3000 g polymer per gram of catalyst.

In another embodiment, the polymerization catalyst and / or catalyst composition, polymerization catalyst and carbonyl compound have a productivity of greater than 2000 g polymer per gram of catalyst, preferably greater than 3000 g polymer per gram of catalyst. Preferably it has a productivity of more than 4000 g of polymer per gram of catalyst, and most preferably a productivity of more than 5000 g of polymer per gram of catalyst.

In one embodiment, the polymerization catalyst and / or catalyst composition generally has a reactivity ratio of less than 2, more typically less than 1. The reactivity ratio is the molar ratio of comonomer to monomer entering the reactor divided by the molar ratio of comonomer to monomer in the polymer product produced, as measured, for example, in the gas composition in a gas phase process. Is defined as In a preferred embodiment, the reactivity ratio is less than 0.6, more preferably less than 0.4, and most preferably less than 0.3. In a most preferred embodiment, the monomer is ethylene and the comonomer is 3
Olefins having more than 4 carbon atoms, more preferably alpha-olefins having more than 4 carbon atoms, and most preferably butene-1, 4-methyl-pentene-1, pentene-1, hexene-1, and octene An alpha-olefin selected from the group consisting of -1.

In another embodiment of the present invention, when converting the first polymerization catalyst to the second polymerization catalyst, the first and second polymerization catalysts are preferably bulky ligand metallocene-type catalyst compounds. Sometimes, more preferably, when the second polymerization catalyst is a crosslinked, bulky ligand metallocene-type catalyst compound, during conversion, it is combined with a crosslinked bulky ligand metallocene-type catalyst. It may be preferable to use a catalyst composition of the carbonyl compound.

When starting a polymerization process, especially a gas phase process, operational problems are more likely to occur. Thus, the present invention contemplates the use of a mixture of a polymerization catalyst and a carbonyl compound at the start to reduce or prevent start-up problems. It is further contemplated that once the reactor is operated at steady state, conversion to the same or different catalyst can take place without the carbonyl compound.

In another embodiment, the polymerization catalyst / carbonyl compound of the present invention was able to migrate during the polymerization process that is or is about to be disrupted. This switching of the polymerization catalyst is intended to be performed when operational problems arise. Symptoms of operational problems are well known in the art. Some of them in the gas phase process include sudden increases in temperature in the reactor, unexpected pressure changes, excessive static electricity generation or abnormally high static electricity spikes, chunking.
), Seating and the like. In one embodiment, the carbonyl compound can be added directly to the reactor, especially when operational problems arise.

The use of a polymerization catalyst in combination with the carbonyl compounds of the present invention is intended to make it easier to produce a fractional melt index and a relatively high density polymer. In one embodiment, the present invention provides a method for polymerizing one or more olefins in a reactor in the presence of a polymerization catalyst combined with a carbonyl compound to provide a melt index of less than about 1 dg / min and a melt index of less than 0.920 g / cc. A method is provided for producing a polymer having a high density, more preferably the polymer has a melt index of less than about 0.75 dg / min and a density of greater than 0.925 g / cc. Preferably, the polymerization catalyst is a bulky ligand metallocene-type catalyst, more preferably the process is a gas phase process, and the polymerization catalyst comprises a support.

The use of the polymerization catalyst / carbonyl compound of the combination of the present invention is intended to make the transition to one of the more difficult grades of polymer easier. Thus, in one aspect, the present invention provides for the polymerization of one or more olefins in the presence of a first catalyst composition under steady state conditions, preferably gas phase process conditions, to form a first olefin.
To a method for producing a polymer product of The first polymer product is 0.87
g / cc, preferably greater than 0.900 g / cc, more preferably 0.9 g / cc.
Densities greater than 10 g / cc and 1 g / min to about 200 dg / min, preferably 1 g / min.
It has a melt index in the range of greater than dg / min to about 100 dg / min, more preferably greater than 1 dg / min to about 50 dg / min, and most preferably greater than 1 dg / min to about 20 dg / min. The process further produces a second polymer having a density greater than 0.920 g / cc, preferably greater than 0.925 g / cc, and a melt index less than 1 dg / min, preferably less than 0.75 dg / min. Transferring to a second catalyst composition for producing the product. The second catalyst composition comprises a combination of a conventional transition metal catalyst and / or a bulky ligand metallocene catalyst and a carbonyl compound. From a first polymer product having less than 25 _I 21 / _{I 2} (as explained later), greater than 25, preferably greater than 30, and more preferably has a large of _I 21 / _{I 2} than 35 Transitioning to a second polymer product is also within the scope of this particular embodiment.

In yet another embodiment, the method of the present invention comprises a first catalyst composition comprising a first polymerization catalyst / carbonyl compound mixture and a carbonyl compound to improve overall process operability. Alternately with the catalyst composition of the second polymerization catalyst not accompanied by In a further aspect, the first and second catalyst compositions described above can be used simultaneously, for example, as a mixture, or can be separately injected into the reactor. In any of these embodiments, the first and second polymerization catalysts may be the same or different.

Polymerization Methods The catalysts and catalyst systems of the present invention described above are suitable for use in any polymerization process over a wide range of temperatures and pressures. The temperature may range from -60 ° C to about 280 ° C, preferably from 50 ° C to about 200 ° C, and the pressure used may range from about 1 atmosphere to about 500 atmospheres or more.

The polymerization methods include solution, gas phase, slurry phase, and high pressure processes, or a combination thereof. Particularly preferred is a gas phase or slurry phase polymerization of one or more olefins, at least one of which is ethylene or propylene.

[0125] In one embodiment, the process of the present invention comprises one of the olefin monomers having 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. The present invention relates to a solution, high pressure, slurry, or gas phase polymerization method. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method comprising the steps of:
It is particularly well suited for the polymerization of more than one olefin monomer.

Other monomers useful in the method of the present invention include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cyclic olefins. . Non-limiting monomers useful in the present invention can include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentene.

In a most preferred embodiment of the process of the present invention, a copolymer of ethylene is prepared, wherein together with ethylene 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, and most preferably 4 to Comonomers having 8 carbon atoms are polymerized in a gas phase process.

In another embodiment of the method of the present invention, ethylene or propylene is polymerized with at least two different comonomers, one of which may optionally be a diene, to form a terpolymer.

In one embodiment, the present invention provides a method for polymerizing propylene alone or with one or more other monomers including ethylene and / or other olefins having 4 to 12 carbon atoms. It relates to a method, in particular a gas or slurry phase method. Polypropylene polymers are disclosed in U.S. Pat. Nos. 5,296,434 and
, 278, 264, both of which are incorporated herein by reference, using a specially bridged bulky ligand metallocene-type catalyst. be able to.

Typically, in a gas phase polymerization process, a continuous cycle is used, in which part of the cycle of the reactor system is a recycle stream or circulating gas, also known as a fluidizing medium. The stream is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor. Generally, in a gas fluidized bed process for making polymers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reaction conditions. A gaseous stream is withdrawn from the fluidized bed and recycled back to the reactor. At the same time, the polymer product is withdrawn from the reactor and new monomer is added to replace the polymerized monomer. (For example, U.S. Pat. Nos. 4,543,399, 4,588,790, and 5,028,67)
No. 5, No. 5,317,036, No. 5,352,749, No. 5,405,92
No. 2, No. 5,436,304, No. 5,453,471, No. 5,462,99
9, No. 5,616,661, and 5,668,228. All of which are fully incorporated herein by reference. )

[0131] Reactor pressure in the gas phase process is from about 100 psig (690 kPa) to about 50 psig.
0 psig (3448 kPa), preferably about 200 ps
sig (1379 kPa) to about 400 psig (2759 kPa), and more preferably from about 250 psig (1724 kPa) to about 350 psi.
g (2414 kPa).

The reactor temperature in the gas phase process can vary from about 30 ° C. to about 120 ° C., preferably from about 60 ° C. to about 115 ° C., and more preferably from about 70 ° C. to 110 ° C. And most preferably in the range of about 70 ° C to about 95 ° C.

Another gas phase method contemplated by the method of the present invention is described in US Pat.
Nos. 7,242, 5,665,818, and 5,677,375, and European Patent Publications EP-A-0 794 200, EP-A-0 802 202, and EP-B-634 421. Including those described, all of which are fully incorporated herein by reference.

In a preferred embodiment, the reactor used in the present invention, and the process of the present invention, is a process wherein the reactor comprises from 500 lbs / hr of polymer (227 Kg / hr) to about 200 lbs / hr.
Up to, 000 lbs / hr (90,900 Kg / hr) or higher, preferably greater than 1000 lbs / hr (455 Kg / hr), more preferably 10,
Greater than 000 lbs / hr (4540 Kg / hr), more preferably 25,000
lbs / hr (11,300 Kg / hr), more preferably 35,000 l
bs / hr (15,900 Kg / hr), more preferably 50,000 lb
s / hr (22,700 Kg / hr), and most preferably 65,000 l
bs / hr (29,000 kg / hr) to 100,000 lbs / hr (45
, 500 Kg / h).

Slurry polymerization processes generally use pressures in the range of about 1 to about 50 atmospheres and even higher, and temperatures in the range of 0 ° C. to about 120 ° C. In a slurry polymerization, a suspension of a solid particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomer and often hydrogen are added along with a catalyst. The suspension containing the diluent is removed intermittently or continuously from the reactor, where the volatile components are separated from the polymer and, if desired after distillation, are recycled to the reactor. The liquid diluent used in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium used must be liquid under the conditions of polymerization and relatively inert. If a propane medium is used, the process must be operated above the critical temperature and pressure of the reaction diluent. Preferably, a hexane or isobutane medium is used.

The preferred polymerization technique of the present invention is referred to as particle form polymerization, or a slurry process where the temperature is maintained below the temperature at which the polymer goes into solution. Such techniques are known in the art and are described, for example, in US Pat. No. 3,248,179, which is fully incorporated herein by reference. Other slurry methods include those using loop reactors and those using multiple stirred reactors in series, parallel, or a combination thereof. Non-limiting examples of slurry methods include continuous loop or stirred tank processes. Other examples of the slurry method are described in U.S. Patent No. 4,613,484, which is fully incorporated herein by reference.

[0137] In one embodiment, the reactor used in the slurry phase method of the present invention comprises:
And the process of the present invention is preferably carried out with a polymer greater than 2000 lbs / hr (907 Kg / hr), more preferably greater than 5000 lbs / hr (2268 Kg / hr), and most preferably greater than 10,000 lbs / hr (4540 Kg / hr). Can be produced. In another embodiment, the slurry phase reactor used in the process of the present invention has a viscosity of greater than 15,000 lbs / hr (6804 Kg / hr), preferably greater than 25,000 lbs / hr (11,340 Kg / hr). Produce polymers up to about 100,000 lbs / hr (45,500 Kg / hr).

Examples of solution methods are described in US Pat. Nos. 4,271,060, 5,001,205,
Nos. 5,236,998 and 5,589,555, which are fully incorporated herein by reference.

A preferred method of the present invention is that the process, preferably a slurry or gas phase process, is carried out in the presence of the bulky ligand metallocene-type catalyst system of the present invention, and triethyl aluminum, trimethyl aluminum, triisobutyl aluminum, And tri-n-
It is operated in the absence or substantially free of scavengers such as hexylaluminum and diethylaluminum chloride, dibutylzinc and the like. This preferred method is described in PCT Publication WO 96/08520 and U.S. Patent Nos. 5,712,352 and 5,763,543, which are fully incorporated herein by reference. ing. In another preferred embodiment of the method of the present invention, the method comprises introducing the carbonyl compound into the reactor and / or prior to introducing into the reactor the carbonyl compound of the present bulky ligand. It is operated by contact with a metallocene type catalyst system. These aspects of the present invention are described in US patent application Ser. No. 09 / 113,216, filed Jul. 10, 1998, which is incorporated herein by reference.

Polymer Products of the Invention The polymers made by the process of the invention can be used in a wide variety of products or end uses. Polymers made by the method of the present invention include linear low density polyethylene, elastomers, plastomers, high density polyethylene, low density polyethylene, polypropylene, and polypropylene copolymers.

These polymers, typically ethylene-based polymers, range from 0.86 g / cc to 0.97 g / cc, preferably from 0.88 g / cc to 0.965 g / c.
c, more preferably 0.900 g / cc to 0.96 g / cc, still more preferably 0.905 g / cc to 0.95 g / cc, even more preferably 0.910 g / cc to 0.95 g / cc. Densities within the range of 0.940 g / cc, and most preferably greater than 0.915 g / cc, more preferably greater than 0.920 g / cc, and most preferably greater than 0.925 g / cc. Have.
Density is measured according to ASTM-D-1238.

The polymers made by the process of the present invention typically have a molecular weight of greater than about 1.5 to about 15, especially greater than 2 to about 10, and more preferably greater than about 2.2 to less than about 8. And most preferably from 2.5 to 8, the molecular weight distribution, ie the ratio of the weight average molecular weight to the number average molecular weight ( _Mw / _Mn ).

In addition, the polymer of the present invention typically has a composition distribution width index (Composite).
ion Distribution Bloodth Index) (CDBI
Has a narrow composition distribution as measured by Details of measuring the CDBI of the copolymer are known to those skilled in the art. For example, P, published on February 18, 1993,
See CT patent application WO 93/03093. This is fully incorporated herein by reference.

In one embodiment, the polymers made with the bulky ligand metallocene-type catalysts of the invention generally range from greater than 50% to 100%, preferably up to 99%, preferably It has a CDBI in the range of 55% to 85%, and more preferably in the range of 60% to 80%, more preferably greater than 60%, and even more preferably greater than 65%.

In another embodiment, the polymer made using the bulky ligand metallocene-type catalyst system of the present invention has less than 50%, more preferably less than 40%, and most preferably less than 30%. CDBI.

In one embodiment, the polymer of the invention is in the range of 0.01 dg / min to 1000 dg / min, more preferably about 0.01 to about 100 dg / min, as measured by ASTM-D-1238-E. , More preferably from about 0.1 dg / min to about 50 dg / min, and most preferably from about 0.1 dg / min to about 10 dg / min.
It has a melt index (MI) or (I ₂ ) in the range of dg / min.

In one embodiment, the polymer of the present invention has a melt index ratio (I ₂₁ / I ₂ ) (I ₂₁ is AS) of less than 10 to less than 25, more preferably less than about 15 to 25.
TM-D-1238-F).

The polymers of the present invention in preferred embodiments preferably have a melt index of greater than 25, more preferably greater than 30, even more preferably greater than 40, even more preferably greater than 50, and most preferably greater than 65. Ratio (I ₂₁ / I ₂ )
(I ₂₁ is measured by ASTM-D-1238-F). In one embodiment, the polymers of the present invention can have a narrow molecular weight distribution and a broad composition distribution, or vice versa, and in US Pat. No. 5,798,427, which is incorporated herein by reference. The polymer described in the above may be used.

In yet another embodiment, a propylene-based polymer is produced in the method of the present invention. These polymers include atactic polypropylene, isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene. Other propylene polymers include propylene blocks or impact copolymers. These types of propylene polymers are well known in the art and are described, for example, in U.S. Patent Nos. 4,794,096 and 3,248,4.
No. 55, No. 4,376,851, No. 5,036,034, and No. 5,459
, 117. All of which are incorporated herein by reference.

The polymers of the present invention can be blended and / or coextruded with other polymers. Non-limiting examples of other polymers include linear low density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene made with conventional Ziegler-Natta and / or bulky ligand metallocene-type catalysts. Including polypropylene.

The polymers and blends made by the method of the present invention are useful in film, sheet, and fiber extrusion and coextrusion, and in molding operations such as blow molding, injection molding, and rotational molding. The film may be used in food contact and non-food applications, including shrink films, adhesive films, stretched films, sealing films, oriented films, snack packaging, sturdy bags, grocery bags, baked and frozen food packaging, Includes blown or cast films formed by coextrusion or lamination, useful as medical packaging, industrial liners, membranes, and the like. Fibers include filters, diaper cloths, medical clothing, geotextiles (ge
melt spinning, solution spinning, and melt blown for use in woven or nonwoven forms to produce textiles, etc.
) Including fiber manipulation. Extruded products include medical tubing, wire and cable coatings, geomembranes, and reservoir liners. Molded products are bottles, tanks, large hollow products,
Includes rigid food containers and toys and other forms of single-layer and multi-layer structures.

[0152] In order to provide a better understanding of the present invention including representative advantages of embodiments the present invention, the following examples are provided.

The catalyst compounds used in the examples were Al Baton Rouge, Louisiana.
Bemarle Corporation available from, dimethylsilyl bis (tetrahydroindenyl) zirconium dichloride _(Me 2 _{Si (H} 4 Ind
) ₂ ZrCl ₂ ). A typical preparation of the polymerization catalyst used in the examples is as follows: (Me ₂ Si (H ₄ Ind) ₂ ZrCl ₂ )
Loaded on 600 ° C. dehydrated Crossfield ES-70 grade silica with a loss on ignition (LOI) of about 1.0% by weight.
LOI is measured by determining the weight loss of a held support material heated to a temperature of about 1000 ° C. for about 22 hours. Crossfield ES-70 grade silica has an average particle size of 40 microns and is available from Cros, Warrington, UK
Available from field Limited.

The first step in the preparation of the supported bulky ligand metallocene-type catalyst described above involves forming a precursor solution. 460 lbs (209 kg) of gas sparged and dehydrated toluene is added to the stirred reactor, followed by 30% by weight methylalumoxane (MAO) in toluene (Albemar, Baton Rouge, Louisiana).
1060 lbs (482 kg) are available. 947 lbs (430 kg) and 600 lbs (272 kg) of a 2 wt% toluene solution of dimethylsilylbis (tetrahydroindenyl) zirconium dichloride catalyst compound
Of additional toluene are introduced into the reactor. Precursor solution at 80 ° F to 100 ° F (
(26.7 ° C to 37.8 ° C) for 1 hour.

While stirring the above precursor solution, 850 lbs (386 kg) of 600 ° C. cross-field dehydrated silica support was slowly added to the precursor solution, and
Stir for 30 minutes between 0 ° F and 100 ° F (26.7 ° C to 37.8 ° C). At the end of the 30 minute agitation of the mixture, Witco Corpo, Memphis, TN
AS-990 (N, N-bis (2-hydroxylethyl) octadecylamine (available as Kemamine AS-990 from E.R.
240% of a 10% by weight toluene solution of (C ₁₈ H ₃₇ N (CH ₂ CH ₂ OH) ₂ )
lbs (109 kg) is added along with an additional 110 lbs (50 kg) toluene rinse, after which the reactor contents are heated to 175 ° F (79 ° C) for 30 minutes.
Mix for a minute. After 30 minutes, vacuum was applied and the polymerization catalyst mixture was allowed to cool to 175 ° F (79 ° C).
) For about 15 hours to dry until a free flowing powder is obtained. Final polymerization catalyst weight is 12
It was 00 lbs (544 kg) and had a Zr wt% of 0.35 and an Al wt% of 12.0.

As shown in the examples below, the carbonyl compound used was
Benzyl (b available from Aldrich, Milwaukee, Wis.
enzil).

Example 1 A 1 liter autoclave equipped with a helical stirrer allowing efficient mixing of solids was charged with 100 g of dry, granular high density polyethylene under a nitrogen atmosphere.
Purging with nitrogen was performed by three pressurizations to 100 psig (689 kPag) and evacuation. To this reactor was then added via syringe 100 mmol of triisobutylaluminum. The reactor was purged with ethylene by three pressurizations and evacuations to 100 psig (689 kPag), then heated to 80 ° C. and brought to a final ethylene pressure of 107 psig (738 kPag).

[0158] 2 "of stainless steel tubing (ball valves) sealed at each end and connected at one end to a source of dry pressurized nitrogen
A 5.1 cm) x 1/4 "(0.64 cm) injection device was charged with 61 mg of supported metallocene catalyst mixed with 6 mg of dry benzyl. The device was connected to the reactor and both The ball valve was opened and the catalyst was injected by flushing the dried catalyst into the reactor with nitrogen.After 30 minutes, the reaction temperature ramped to 100 ° C. and was held for another 30 minutes. Evacuated, cooled, and recovered resin, a total of 26.2 g of fresh resin was produced.After sieving through a 10 mesh screen, 3.1 g of resin remained on the screen (coarse pieces). (
rubble)).

Example 2 The procedure was entirely the same as in Example 1 except that benzyl was not mixed with the catalyst and instead 12 mg of benzyl were charged to the bed of granular high-density polyethylene immediately before the addition of triisobutylaluminum. It was the same.

Example 3 The procedure was exactly the same as in Example 2, except that 30 mg of benzyl was charged to the bed of high-density polyethylene immediately before the addition of the triisobutylaluminum.

Example 4 The procedure was exactly the same as in Example 3, except that after the reaction had proceeded for 20 minutes, 30 mg of benzyl were added using the injector.

Example 5 The procedure was exactly as in Example 1, except that 9-fluorinone was used instead of benzyl.

Example 6 The procedure was exactly the same as in Example 1, except that 2-carboxybenzaldehyde was used instead of benzyl.

Comparative Examples 7-15 (CEx 7-15) The procedure was exactly the same as in Example 1, except that benzyl was not used.

Table 1 below sets forth the rubble and flake weight% produced in each of Examples 1-6 and Comparative Examples 7-15 above. The higher the level of flakes produced, the worse the operability of the method of the invention.

[0166]

[Table 1]

From the data provided in Table 1 above, the use of the carbonyl compounds of the present invention
Provide an improved polymerization process that produces a minimum amount of flakes.

Example 14 2-Ethyl-anthraquinine was used in place of benzyl, except that the temperature was ramped from 90 ° C to 110 ° C instead of from 80 ° C to 100 ° C. The procedure was exactly the same as in Example 1.

Comparative Examples 15 and 16 (CEx 15-16) The procedure was as in Example 14 except that no 2-ethylanthraquinone was used.
It was exactly the same.

Table 2 below sets forth the flakes and flake weight percent, the higher the level of flakes produced, the worse the operability of the method of the present invention.

[0171]

[Table 2]

While the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will appreciate that the invention is also directed to variations that are not necessarily illustrated herein. right. For example, it is contemplated that carbonyl compounds can be added to the reactor in addition to contacting with the catalyst system of the present invention. It is also contemplated that the method of the present invention can be used in a continuous reactor polymerization process. For example, a supported bulky ligand metallocene-type catalyst system containing no carbonyl compound is used in one reactor, and the supported, crosslinked bulky ligand metallocene contacted with the carbonyl compound is used. Type catalyst system is used in another reactor or vice versa. It is also contemplated that the carbonyl compound can be separately supported on a different carrier than the polymerization catalyst, preferably the supported polymerization catalyst. For this reason, for the purpose of determining the true scope of the invention, reference should only be made to the appended claims.

────────────────────────────────────────────────── ─── Continued on the front page (31) Priority claim number 09 / 392,417 (32) Priority date September 9, 1999 (September 9, 1999) (33) Priority claim country United States (US) ( 81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AU, BR, CA, CN, CZ, JP, KR, MX, NO, PL, RU, SG, ZAF terms (reference) 4J011 AA01 AA04 BA01 BB02 BB03 BB05 DA03 DA06 DB11 DB13 DB23 DB32 EA03 EA06 EA09 JB12 JB22 MA02 MA06 MA15 MA18 MA19 MB01 NC01 PA27 4J028 AA01A AB00A AB01A AC01A AC04A AC05A AC06A AC10A AC15A AC23A AC28A AC34A AC35A AC36A AC42A 1B BC03B BC04B BC05B BC06B BC09B BC12B BC15B BC16B BC27B BC40B CB42C CB43C CB44C CB52C CB53C CB54C EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB10 EB12 EB15 FA01 FA02 FA04 AC04 AC07 AC01 AC09 GA09 AC47 AD00 BC01B BC03B BC04B BC05B BC06B BC09B BC12B BC15B BC16B BC27B BC43B CB42C CB43C CB44C CB52C CB53C CB54C EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB12 EB15 FA01 FA02 FA04 FA07 GA07

Claims (50)

[Claims] 1. A catalyst composition comprising a combination of a polymerization catalyst and a carbonyl compound. 2. The catalyst composition of claim 1, wherein the polymerization catalyst comprises a conventional transition metal catalyst compound. 3. The catalyst composition according to claim 1, wherein the polymerization catalyst comprises a bulky ligand metallocene-type catalyst compound. 4. The carbonyl compound is represented by the general formula: R (C ＝ O) _n R ′, wherein n is 1 or 2, and R and R ′ may be the same or different; 2. The catalyst composition of claim 1, having up to 100 non-hydrogen atoms. 5. The catalyst composition of claim 4, wherein n is 2 and R and R ′ are the same or different and have 1 to 50 carbon atoms. 6. The catalyst composition according to claim 1, wherein the carbonyl compound is a diketone. 7. The catalyst composition according to claim 1, wherein the carbonyl compound is an aldehyde. 8. The catalyst composition according to claim 1, wherein the polymerization catalyst comprises a carrier. 9. The catalyst composition of claim 1, wherein the weight percent of the carbonyl compound based on the total weight of the polymerization catalyst ranges from 0.1% to about 100% by weight. 10. A method for producing a catalyst composition, comprising the steps of: (a) a polymerization catalyst; and (b) a carbonyl compound. 11. The polymerization catalyst according to claim 1, wherein the polymerization catalyst comprises a conventional transition metal catalyst compound.
0 method. 12. The method of claim 10, wherein the polymerization catalyst comprises a bulky ligand metallocene-type catalyst compound. 13. The method of claim 10, wherein the polymerization catalyst comprises a support. 14. The carbonyl compound is represented by the formula: R (C ＝ O) _n R ′, wherein n is 1 or 2, and R and R ′ may be the same or different, 11. The method of claim 10, having up to non-hydrogen atoms. 15. The method of claim 14, wherein n is 2. 16. The method of claim 10, wherein the weight percent of the carbonyl compound based on the total weight of the polymerization catalyst ranges from 0.1% to about 100% by weight. 17. The method of claim 10, wherein the weight percent of carbonyl compound based on the total weight of the supported bulky ligand metallocene-type catalyst system is in the range of about 0.5 to about 25% by weight. . 18. The method of claim 10, wherein the carbonyl compound has a melting point above 50 ° C. 19. The method of claim 10, wherein the mixing time is from 10 minutes to about 48 hours. 20. A process for polymerizing one or more olefins in a reactor in the presence of a catalyst composition comprising a polymerization catalyst that has been contacted with a carbonyl compound prior to introduction into the reactor. 21. The method of claim 20, wherein the polymerization catalyst comprises a bulky ligand metallocene-type catalyst compound. 22. The polymerization catalyst according to claim 2, wherein the polymerization catalyst comprises a conventional transition metal catalyst compound.
0 method. 23. The carbonyl compound is represented by the general formula: R (C = O) _n R ′, wherein n is 1 or 2, and R and R ′ may be the same or different; 21. The method of claim 20, having up to 100 non-hydrogen atoms. 24. A polymerization catalyst comprising an inorganic carrier and a bulky ligand metallocene-type catalyst compound, wherein the weight percentage of the carbonyl compound based on the total weight of the polymerization catalyst ranges from about 0.1 to about 50% by weight. 21. The method of claim 20, wherein 25. A gas or slurry phase process for polymerizing one or more olefins in a reactor in the presence of a catalyst composition, wherein the catalyst composition comprises at least one polymerization catalyst and at least one carbonyl. A method comprising the compound. 26. The method of claim 25, wherein the method is a gas phase process and the reactor is a fluidized bed reactor. 27. The method of claim 25, wherein said at least one polymerization catalyst comprises a bulky ligand metallocene-type catalyst compound and an activator. 28. The method according to claim 1, wherein the density is greater than 0.920 g / cc and about 1 dg / cc.
26. The method of claim 25, wherein the method produces a polymer product having a melt index of less than one minute. 29. The method according to claim 1, wherein the method has a density higher than 0.925 g / cc and 0.75 d.
3. A polymer product having a melt index of less than g / min.
Method 5. 30. The method of claim 25, wherein the method produces more than 1000 lbs (455 Kg) of polymer per hour. 31. The method of claim 25, wherein the method produces a polymer product having an I ₂₁ / I _{2 of} greater than 30. 32. The weight percent of the at least one carbonyl compound is greater than 1 based on the total weight of the at least one polymerization catalyst, and the polymer product has a density greater than 0.910 g / cc. Item 25. The method according to Item 25. 33. A continuous gas phase process for polymerizing one or more monomers in a reactor, the process comprising: (a) introducing a recycle stream to the reactor, wherein the recycle stream is (B) introducing a polymerization catalyst and a carbonyl compound into the reactor, (c) extracting a recycle stream from the reactor, (d) cooling the recycle stream, e) introducing additional monomer into the reactor to replace the polymerized monomer; (g) re-introducing the recycle stream into the reactor; and (h) withdrawing the polymer product from the reactor; Including, methods. 34. The method of claim 33, wherein the polymerization catalyst comprises a bulky ligand metallocene-type catalyst compound and an activator. 35. The method of claim 33, wherein the polymerization catalyst and the carbonyl compound are introduced into the reactor continuously or intermittently. 36. The method of claim 33, wherein the polymerization catalyst and the carbonyl compound are combined to form a catalyst composition, after which the catalyst composition is introduced into the reactor. 37. The carbonyl compound is represented by the general formula: R (C ＝ O) _n R ′, wherein n is 1 or 2, and R and R ′ may be the same or different; 34. The method of claim 33, having up to 100 non-hydrogen atoms. 38. The method of claim 37, wherein n is 2. 39. The method of claim 37, wherein the carbonyl compound is a diketone. 40. The method of claim 33, wherein the carbonyl compound is an aldehyde. 41. A method of polymerizing one or more olefins in a reactor in the presence of a catalyst composition, wherein the catalyst composition comprises a polymerization catalyst, and (a) reacting the first carbonyl compound in the reactor. And (b) introducing the catalyst composition after step (a) into the reactor, and / or
And) simultaneously introducing the catalyst composition into the reactor. 42. The method of claim 41, wherein the catalyst composition further comprises a second carbonyl compound. 43. The method of claim 41, wherein the polymerization catalyst comprises a bulky ligand metallocene-type catalyst compound and an activator. 44. The method of claim 43, wherein a polymerization catalyst is supported. 45. The first carbonyl compound is represented by the general formula: R (C = O) _n R ', wherein n is 1 or 2 and R and R' are the same or different. 44. The method of claim 43, which has up to 100 non-hydrogen atoms. 46. The method of claim 41, wherein said first carbonyl compound is a diketone. 47. The method of claim 41, wherein the first carbonyl compound is an aldehyde.
the method of. 48. The method of claim 42, wherein the second carbonyl compound is different from the first carbonyl compound. 49. The method of claim 45, wherein n is 2. 50. The method of claim 45, wherein R and R 'have 1 to 50 carbon atoms.